5-(2-Chloro-4-trifluoromethyl)-, or (4-trifluoromethyl or 2,6-dichloro-4-trifluoromethylphenoxy)-2-nitro-substituted carbonyl oxime-O-alkyl ethers

ABSTRACT

Disclosed are compounds such as 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-methyl ether, and the method of controlling weeds, such as wild oats with the compounds.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention pertains to 5-(4-trifluoromethyl, or(2-chloro-4-trifluoromethyl) or(2,6-dichloro-4-trifluoromethylphenoxy-2-nitro substituted carbonyloxime-O-alkyl ethers, such as5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-acetaphenoneoxime-O-methyl ether and their use to control weeds, i.e., wild oats.

2. Description of the Prior Art

The prior art describes diphenyl ethers in general. The prior art,however, is silent concerning the novel compounds of this invention andtheir use as preemergence herbicides against certain weeds andpostemergence herbicides against weeds.

SUMMARY OF THE INVENTION

The invention concerns novel herbicidal compounds graphicallyrepresented by general Formula I ##STR1## wherein: Y is chlorine orhydrogen; Z is chlorine when Y is chlorine, or Z is hydrogen when Y ischlorine or hydrogen; R is hydrogen or an alkyl of up to three carbonatoms, and R¹ is an alkyl of up to four carbon atoms; as well as themethod of preparing these novel compounds and the control of weeds withthe compounds; for example5-(2-chloro-4-trifluorophenoxy)-2-nitroacetophenone oxime-O-methyl etherin its anti and syn isomer forms is useful for controlling the weedsdescribed herein.

DETAILED DESCRIPTION OF THE INVENTION

The novel agriculturally useful 5(2-chloro-4-trifluoromethyl- or4-trifluoromethyl or2,6-dichloro-4-trifluoromethylphenoxy)-2-nitro-substituted carbonyloxime alkyl ethers in both their anti and syn forms are graphicallyrepresented by general Formula I wherein: ##STR2## Y is chlorine orhydrogen; Z is chlorine when Y is chlorine, or Z is hydrogen when Y ischlorine or hydrogen;

R is hydrogen or an alkyl of up to three carbon atoms, and

R¹ is an alkyl of up to four carbon atoms.

Representative compounds are those in which

I. R is an alkyl of up to three carbon atoms; such as

5-(4-trifluoromethylphenoxy)-2-nitrobutyrophenone oxime-O-t-butyl ether,

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-2-methylpropiophenoneoxime-O-sec butyl ether,

5-(2,6-dichloro-4-trifluoronethylphenoxy)-2-nitro butyrophenoneoxime-O-isopropyl ether,

5-(4-trifluoromethylphenoxy)-2-nitropropiophenone oxime-O-propyl ether,

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiophenoneoxime-O-methyl ether,

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-ethylether,

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenoneoxime-O-isobutyl ether,

5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroacetophenoneoxime-O-propyl ether,

II. R is hydrogen; such as:

5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-O-t-butyl ether,

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-O-methylether,

5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-O-ethylether,

5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-O-propyl ether.

As used herein and in the claims, the word "compound" and the name ofcompound, for example5-(2-chloro-4-trifluorophenoxy)-2-nitroacetophenone oxime-O-methylether, refers to the two isomers of the compound, the syn and antiisomers.

Although all the compounds as disclosed herein are useful for thepurposes disclosed herein, some compounds are preferred over others.Those compounds in which R is methyl are preferred to those compounds inwhich R is hydrogen or an alkyl of from two to three carbon atoms. Thosecompounds in which Y and Z are as mentioned herein, in order ofincreasing preference are; those in which Y and Z are hydrogen, those inwhich Y and Z are chlorine, and those in which Y is chlorine and Z ishydrogen. Those compounds in which R¹ is methyl or ethyl are greatlypreferred.

The highly preferred compounds graphically represented by generalFormula I are:

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-O-methylether,

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro benzaldoxime-O-ethylether,

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-ethylether, and

5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-methylether.

The most preferred compound is5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-methylether.

SYNTHESIS a. GENERAL PROCEDURE

The synthesis of the 5-(substituted-phenoxy)-2-nitro substitutedcarbonyl oxime ethers, described herein proceeds according to thereaction equations (1), (2), (3) and (4) shown below:

The appropriate trifluoromethyl halo substituted compound of Formula Vwhere Y and Z are as described herein is reacted with a salt of ametal-3-substituted carboxyl phenoxide of Formula VI, where M is acation of sodium, (Na+), potassium (K+) to form a compound of FormulaVII, which is separated from the reaction mixture and nitrated to acompound of Formula II. Note the step of nitrating also includes thestep of separating the compound of Formula VI from the nitratingreaction mixture. ##STR3##

The appropriate carbonyl compound (aldehyde) graphically represented bygeneral Formula II wherein Y and Z, are as defined herein and R ishydrogen; for example (0.001 mole) is dissolved in 20 milliliters oftetrahydrofuran (THF) and 12 milliliters of absolute ethanol. To thisstirred solution is added hydroxylamine hydrochloride (0.012 mole) in 1milliliter of water, and then 0.6 grams (0.015 mole) sodium hydroxide in5 milliliters of water. The solution is stirred overnight at ambienttemperature and the THF and ethanol is stripped off in vacuo, leaving atwo-phase system. The oil phase is dissolved in chloroform (HCCl₃) andthen separated from the aqueous phase. The chloroform layer is thenextracted with water, and with a saturated sodium chloride solution, andthen dried over anhydrous magnesium sulfate (MgSO₄). Filtration andevaporation affords the crude product of 5-(2-chloro-4-trifluoromethyl-,or 4-trifluoromethyl- or 2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrosubstituted carbonyl oximes of general Formula III wherein Y, Z, and Rare as defined herein. The crude product can be recrystallized in carbontetrachloride (CCl₄).

An alternate procedure is used when R of Formula II is an alkyldescribed herein. This procedure employs anhydrous conditions. Forexample, (0.0056 mol) of the appropriate carbonyl compound of generalFormula II, wherein Y and Z are as defined herein and R is an alkyldefined herein, is dissolved in 20 ml. of a 1:1 mixture of absoluteethanol and dry benzene. To this solution is added 0.77 grams ofhydroxylamine hydrochloride in 15 ml. of absolute ethanol and (0.0112mol) of a tertiary amine, such as triethylamine, which is preferred. Thesolution is heated to reflux and the water formed in the reaction isazeotroped off. After refluxing for 18 hours, solvent is removed invacuo, the residue dissolved in chloroform and extracted with water andsaturated sodium chloride solution and dried over anhydrous magnesiumsulfate. Filtration and evaporation affords the crude product oximes ofgeneral Formula III.

The appropriate oxime of general Formula III, prepared as above, (0.004mole) is dissolved in four milliliters of ethanol and added to asolution of 0.1 gram (0.0045 mole) of the appropriate halo-alkylcompound of general Formula IV wherein R¹ is as defined herein, and A ischlorine, bromine, or iodine, and the reaction is followed by thin layerchromatography. The solution can be heated at reflux, if the reaction issluggish. The product of general Formula I is obtained either byfiltration or by evaporating the solvent, dissolving the residue inchloroform, extracting with water, drying and then evaporating thechloroform solvent.

Sodium hydride can be used in place of the sodium alkoxide, and thesolvent can be an ether such as THF or diethyl ether, etc.

b. EXAMPLES

The following example illustrates the synthesis of the compound ofgeneral Formula I by the general procedure described above.

EXAMPLE I Synthesis of5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime-O-methylether a. Preparation of3-(2-chloro-4-trifluoromethylphenoxy)acetophenone.

To a 250 ml. flask containing a solution of 13.92 grams of the potassiumsalt of 3-hydroxyacetophenone in 30 ml. of dry dimethylsulfoxide (DMSO),was added 17.12 grams (0.08 mole) of 3,4-dichlorobenzotrifluoride. Thereaction solution was heated to 175° Centigrade for six hours, and thencooled and stirred at ambient temperature for 18 hours. The bulk of theDMSO was removed by evaporation, and the remaining dark residue wasstirred with diethyl ether for 15 minutes and filtered. The filtrate wasextracted once with wter, once with sodium hydroxide, once with asaturated sodium chloride solution, dried over anhydrous MgSO₄,filtered, decolorized with charcoal, and evaporated to dryness leaving16.04 grams of a dark red oil of3-(2-chloro-4-trifluoromethylphenoxy)acetophenone. The material wasfurther purified by passing through a neutral, grade III alumina column.

b. Nitration of 3-(2-chloro-4-trifluoromethylphenoxy)acetophenone

To a 100 milliliter (ml.) flask containing a solution of 26 ml. ofconcentrated sulfuric acid (H₂ SO₄), and 16 ml. of ethylenedichloride(EDC), which was cooled to zero (0°) degrees Centigrade, 6.28 grams,(0.02 mole) of the dark red oil of3-(2-chloro-4-trifluoromethylphenoxy)acetophenone (prepared as describedherein) was added dropwise to form a brownish-black solution. When theaddition of 3-(2-chloro-4-trifluoromethylphenoxy)acetophenone wascompleted, dry potassium nitrate (KNO₃), (2.0 grams, 0.020 mole) wasadded in small portions over a 20 minute period so as to maintain thereaction mixture below 4° Centigrade. The reaction mixture was stirredfor 0.5 hours at 0° Centigrade. It was then poured into 250 ml. of iceand water, and the resulting mixture was mixed with 200 ml. ofchloroform, (CHCl₃). The organic layer was separated, and then extractedtwice with water, once with a saturated sodium chloride solution, andthen dried over anhydrous magnesium sulfate, and then filtered. Theorganic solvent was evaporated off to yield 6.51 grams of an orange oilwhich analysis showed was a mixture of two positional isomers, one ofwhich was 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone. Themixture was separated into two fractions by high pressure liquidchromatography (HPLC) using diethyl ether as the eluant.

The diethylether was stripped from fraction #1, leaving 2.37 grams of anorange oil of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone.

Nuclear magnetic resonance [(NMR) (CDCl₃)]: 2.47δ (sing., 3H),6.78-8.21δ (mult. 6H); Infra Red (IR): 1710, 1575, 1520, 1400, 1315 cm⁻¹; Mass Spectra (MS) molecular ion at m/e 359.

c. Synthesis of5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenoneoxime

A 100 ml. flask was charged with a solution of 2.0 grams (0.0056 mole)of the orange oil,5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone, in 10 ml. ofabsolute ethanol and 10 ml. of dry benzene. A solution of hydroxylaminehydrochloride (0.77 grams, 0.011 mole) in 15 ml. of absolute ethanol wasadded followed by addition of 1.12 grams (0.011 mole) of an acidacceptor triethylamine. The reaction mixture was then refluxed; when 20ml. of solvent was distilled off, an additional 15 ml. of benzene wasadded. Refluxing was continued until 15 ml. of solvent distilled off,and then the remaining solution was refluxed for 16 hours, with theformation of a mixture of the syn and anti isomers of5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime. Thesolvent was stripped from the mixture, and the residue was dissolved inchloroform. The chloroform solution was extracted twice with water, thenwith a saturated solution of sodium chloride, and then dried overanhydrous magnesium sulfate.

The chloroform solution was filtered and the solvent (chloroform) wasevaporated to yield 2.03 grams of an orange oil of5-(2-chloro-4-trifluoromethylpehnoxy)-2-nitroacetophenone oxime (antiand syn), which had the following:

Mass spectra (MS): molecular ion at m/e 374.

Syn and Anti NMR (CDCl₃): 2:138δ (sing., 3H), 6.91-8.178δ (mult., 6-H),9.338δ (sing., 1H).

Syn and Anti IR: 3100 broad, 1605, 1575, 1520, 1400 cm⁻¹.

d. Formation of the anti and syn Isomers of5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro acetophenoneoxime-O-methyl ether

A solution of 0.10 grams (0.0045 ml.) of sodium metal in 5 ml. ofmethanol under nitrogen was charged into a 25 ml. flask. When all of thesodium had reacted, 1.50 grams (0.004 mole) of the5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenone oxime (antiand syn) prepared as described, and dissolved in 3 ml. of methanol wasadded, and the solution stirred. Methyliodide (0.64 grams, 0.0045 mole)was added next to the solution; and the resulting mixture was stirred atambient temperature under nitrogen for forty-two (42) hours. The solventwas stripped from the solution and the residue was dissolved inmethylene chloride (CH₂ Cl₂). The CH₂ Cl₂ solution was extracted twicewith water and once with a saturated sodium chloride solution, and thendried over anhydrous magnesium sulfate. The CH₂ Cl₂ solution was thenfiltered and the solvent removed by evaporation to yield 1.84 grams ofan orange oil containing the anti and syn isomers of5-(2-chloro-4-trifluoromethylphenoxy)- 2-nitro acetophenoneoxime-O-methyl ether. The orange oil was purified by chromatography bydissolving it into 5 ml. of ethyl ether and placing it on top of aneight inch by 21 mm. column of grade III alumina. The column was elutedwith diethyl ether and the desired fractions were collected. The solventwas removed to yield 0.49 grams of a yellow oil of anti and syn isomersof 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-0-acetophenone oxime.

MS: Molecular ion at m/e. 388.

Syn and Anti IR: 2965, 1605, 1570, 1520, 1400 cm⁻¹.

Syn and Anti NMR (CDCl₃): 2.31δ and 2.25δ (sing., 3H), 3.69δ and 3.91(sing., 3H), 6.85-8.19δ (mult.6H).

APPLICATIONS OF THE COMPOSITIONS AGAINST WEEDS

The novel compounds of this invention are particularly valuable forpreemergence and postemergence weed control because they are toxic tomany species and groups of weeds and are relatively nontoxic to manybeneficial plants. The exact amount of one or more of the compoundsdescribed herein required depends upon a variety of factors, includingthe hardiness of the particular weed species, the weather, the type ofsoil, the method of application, the kind of beneficial plants in thesame area, and the like. Thus, while the application of up to only about0.1 pounds of active compound per acre may be sufficient for goodcontrol of a light infestation of weeds growing under adverseconditions, the application of 2 pounds or more of an active compoundper acre may be required for good control of a dense infestation ofhardy perennial weeds growing under favorable conditions. The preferredcompounds mentioned herein are generally used at the lower applicationrates such as from 0.1 to 10 pounds per acre; the less preferred butgenerally useful compounds are generally applied at the higherapplications of from 10 to 20 pounds per acre, and those compounds whichare intermediate between the most preferred compounds and the generallyuseful compounds are generally applied at rates from 5 to 15 pounds peracre.

a. Examples of Weeds Which May Be Controlled By The Compounds DescribedHerein

Weeds are undesirable plants growing where they are not wanted and maybe classified as broadleaf or grassy weeds, a classification whichincludes many types of known weeds. It is believed that many weeds maybe controlled by the compositions set forth herein, when applied in aherbicidally effective amount. These include field pennycress, ryegrass,goosegrass, chickweed, purslane, smartweed, knotweed, wild buckwheat,kochia, medic, corn cockle, ragweed, sow-thistle, croton, cuphea,dodder, fumitory, groundsel, hempnettle, knawel, spurge, spurry, emex,jungle rice, pondweed, dogfennel, carpetweed, bedstraw, ducksalad,naiad, cheatgrass, fall panicum, witchgrass, switchgrass, watergrass,teaweed, wild turnip, and sprangletop; biennials such as wild carrot,matricaria, wild barley, campion, chamomile, burdock, mullein,roundleaved mallow, bull thistle, houndstongue, moth mullein, and purplestar thistle; or perennials such as white cockle, perennial ryegrass,quackgrass, Canada thistle, hedge bindweed, Bermuda grass, sheep sorrel,curly dock, nutgrass, field chickweed, dandelion, campanula, fieldbindweed, Russian knapweed, mesquite, toadflax, yarrow, aster, gromwell,horsetail, ironweed, sesbania, bulrush, cat-tail, wintercress,horsenettle, nutsedge, milkweed, and sicklepod.

The genus of weeds the compounds, particularly the most preferredcompounds, appear most active against preemergence are: Sorghum,Sesbania, Fatua and Echinochola.

Weed species against which the compounds of the invention appear to bemost effective (preemergence) are: Sorghum halepense (johnsongrass),Sesbania spp. (coffeeweed), Avena fatus (L) (wild oats), and Echinocholacrusgalli (L) (barnyard grass).

The genus of weeds that the compounds, particularly the most preferredcompounds, appear most active against postemergence are: Sida, Datura,Brassica, Setaria, Gossypium, Sorghum, Sesbania, Abutilon, Ipomoea,Avena, and Echinochola.

The compositions, particularly, the most preferred compositions, appearto be most effective when applied postemergence against the weed speciesSida spinosa (L) (teaweed, prickly sida), Datura stramonium (L)(jimsonweed), Brassica kaber (DC) (wild mustard), Setaria glauca (L)(yellow foxtail), Gossypium hirsutum (L) (cotton), Sesbania spp.(coffeeweed), Abutilon theophrasti (L) (velvetleaf), Ipomoea purpurea(L) Roth (tall morningglory), Sorghum halepense (johnsongrass), Avenafatua (L) (wild oats) and Echinochola crusgalli (L) (barnyard grass).

b. Description of the Method of Controlling Weeds

As used herein and in the claims, the method of controlling the weedscomprises contacting the weeds with a herbicidally effective amount of acomposition represented by the general formula described herein. Theterm "contacting the weeds" refers to any method of contacting theweeds, both preemergence (before the weeds appear) and/or postemergence(after the weeds appear), such as applying granules of the compound tothe soil prior to emergence, or spraying a solution of the compound orcompounds described by the general formula, or any other method known inthe art by which the weeds are contacted either before they emerge orafter they emerge, or both before and after they emerge, but preferablyafter they emerge, with one or more of the compounds represented byFormula I described herein. The phrase "the herbicidally effectiveamount" refers to that amount required under the environmentalconditions in order to effectively control, that is, by which the weedsare killed or are injured so severely as not to be able to recover fromthe application of the compound.

c. GENERAL APPLICATION OF THE COMPOUNDS

For practical use as herbicides, the compounds of this invention aregenerally incorporated into herbicidal formulations which comprise aninert carrier and a herbicidally toxic amount of a compound mentionedherein. Such herbicidal formulations enable the active compound to beapplied conveniently to the side of the weed infestation in any desiredquantity. These formulations can be solids such as dusts, granules, orwettable powders or they can be liquids such as solutions, aerosols, oremulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the talcs, clays, silicas,pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5millimeters. Wettable powders, which can be dispersed in water or oil toany desired concentration of the active compound, can be prepared byincorporating wetting agents into concentrated dust compositions.

In some cases, the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofherbicides can be dispersed under superatmospheric pressure as aerosols.However, preferred liquid herbicidal formulations are emulsifiableconcentrates, which comprise an active compound according to thisinvention and as the inert carrier, a solvent and an emulsifier. Suchemulsifiable concentrates can be extended with water and/or oil to anydesired conentration of active compound for application as sprays to thesite of the weed infestation. The emulsifiers most commonly used inthese concentrates are nonionic or mixtures of nonionic with anionicsurface-active agents. With the use of some emulsifier systems aninverted emulsion (water in oil) can be prepared for direct applicationto weed infestations.

A typical herbicidal formulation according to this invention isillustrated by the following example, in which the quantities are inparts by weight.

EXAMPLE III Preparation of a Dust

Product of Example I: 10

Powdered Talc: 90

The above ingredients are mixed in a mechanical grinder-blender and areground until a homogeneous, freeflowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the weed infestation.

d. Use of Compounds Alone Or In Mixtures

Although all of the compounds described herein and represented by thegeneral formula described herein are useful as herbicides, some of theseare preferred and are better for applications against weeds. In general,all of the compounds described herein may be used either alone ortogether in mixtures of the compounds described herein. When used inmixtures the amount of ratio of one compound to another may vary from0.01 to 100. The amount to use ranges from 0.10 pounds per acre to 20pounds per acre depending upon the conditions.

e. Manner of Application Of The Compounds Of This Invention InFormulations

The compounds of this invention can be applied as herbicides in anymanner recognized by the art. One method for the control of weedscomprises contacting the locus of said weeds with a herbicidalformulation comprised of an inert carrier and one or more of thecompounds of this invention as an essential active ingredient, in aquantity which is herbicidally toxic to said weeds. The concentration ofthe new compounds of this invention in the herbicidal formulations willvary greatly with the type of formulation and the purpose for which itis designed, but generally the herbicidal formulations will comprisefrom about 0.05 to about 95 percent by weight of the active compounds ofthis invention. In a preferred embodiment of this invention, theherbicidal formulations will comprise from about 5 to 75 percent byweight of the active compound. The formulations can also comprise otherpesticides, such as insecticides, nematocides, fungicides, and the like;stabilizers, spreaders, deactivators, adhesives, stickers, fertilizers,activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other herbicides and/or defoliants, desiccants, growth inhibitors,and the like in the herbicidal formulations heretofore described. Theseother materials can comprise from about 5 percent to about 95 percent ofthe active ingredients in the herbicidal compositions. Use ofcombinations of the present invention provide herbicidal formulationswhich are more effective in controlling weeds and often provide resultsunattainable with separate formulations of the individual herbicides.

f. Examples of Other Pesticides And Herbicides For Combinations

The other herbicides, defoliants, desiccants, and plant growthinhibitors, with which the compounds of this invention can be used inthe herbicidal formulations to control weeds, can include: chlorophenoxyherbicides; such as 2,4-D, 2,4,5-T, MCPA, NCPB, 4-2,4-DB, 2,4-DEB,4-CPB, 4-CPA, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and the like;carbamate herbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC,and the like; thiocarbamate and dithiocarbamate herbicides such as CDEC,metam sodium, EPTC, diallate, PEBC, perbulate, vernolate and the like;substituted urea herbicides such as norea, siduron, dichloroal urea,chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron,monolinuron, neburon, buturon, trimeturon, and the like; symmetricaltriazine herbicides such as simazine, chlorazine, desmetryne, norazine,ipazine, prometryn, atrazine, trietazine, simetone, prometone,propazine, ametryne, and the like; chloroacetamide herbicides such asalpha-chloro-N,N-dimethylacetamide, CDEA, CDAA,alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide,4-(chloroacetyl) morpholine, 1-(chloroacetyl) piperidine, and the like;chlorinated aliphatic acid herbicides such as TCA, dalapon,2,3-dichloropropionic acid, 2,2,3-TPA, and the like; chlorinated benzoicacid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6TBA,dicamba, tricamba, amiben, fenac, PBA,2-methoxy-3,5-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2-methoxy-3,5,6-trichlorophenylacetic acid,2,5-dichloro-3-nitrobenzoic acid, dual metribuzin and the like; and suchcompounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate,endothall, biuret, technical chlordane, dimethyl2,3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, DNBP, dichlobenil,DPA, diphenamid, dipropalin, trifluralin, solan, dicryl, merphos, DMPA,DSMA, MSMA, potassium azide, acrolein, benefin, bensulfide, AMS,bromacil, 2-(3,4-dichlorophenyl)-4methyl-1,2,4-oxadiazolidine-3,5-dione,bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone,dipheratril, DMTT, DNAP, EXD, ioxynil, isocil, potassium cyanate, MAA,MAMA, MCPES, MCPP, MH, molinate, NPA, paraquat, PCP, picloram, DPA, PCA,pyrichlor, sesone, terbacil, terbutol, TCBA, LASS0, planavin, sodiumtetraborate, calcium cyanamide, DEF, ethyl xanthogen disulfide, sindone,sindone B, propanil, and the like. Such herbicides can also be used withthe compositions of this invention in the form of their salts, esters,amides, and other derivatives whenever applicable to the particularparent compounds.

g. Examples of Herbicidal Control

The following examples illustrate the utility of the compositionsdescribed herein for the control of weeds.

These tests described herein were conducted in a laboratory underlaboratory conditions in accordance with standard herbicidal testingprocedures for preemergence and postemergence control. The plants areobserved for 21 days after treatment, and the observations wererecorded.

EXAMPLE II

When 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenoneoxime-0-methyl ether (from Example I) was applied preemergence at ten(10) pounds per acre to Sorghum halepense (L) (johnsongrass--from seed);Sesbania spp. (coffeeweed), Avena fatua (L) (wild oats), and Echinocholacrusgalli (L) (barnyard grass), the weeds were killed by 21 days.

EXAMPLE III

When 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenoneoxime-0-methyl ether (from Example I) was applied postemergence at ten(10) pounds per acre to: Sida spinosa (L) (teaweed, also called pricklysida); Datura stramonium (jimsonweed), Brassica kaber (wild mustard),Setaria glauca (L) (yellow foxtail), Gossypium hirsutum (cotton),Sesbania spp. (coffeeweed), Abutilon theophrasti (velvetleaf), Ipomoeapurpurea (L) Roth (tall morningglory), Sorghum halephense(johnsongrass), Avena fatua (L) (wild oats), and Echinochola crusgalli(L) (barnyard grass), all the weeds were killed by 21 days.

While the invention has been described with reference to specificdetails of certain illustrative embodiments, it is not intended that itshall be limited thereby except insofar as such details appear in theaccompanying claims.

I claim:
 1. A compound graphically represented by general Formula I##STR4## wherein: Y is chlorine or hydrogen;Z is chlorine when Y ischlorine, or Z is hydrogen when Y is chlorine or hydrogen; R is hydrogenor an alkyl of up to three carbon atoms; and R¹ is an alkyl of up tofour carbon atoms.
 2. The compound as recited in claim 1 wherein R ishydrogen.
 3. The compound as recited in claim 2 wherein R¹ is an alkylselected from the groups consisting of methyl and ethyl.
 4. The compoundas recited in claim 1, wherein R¹ is an alkyl of up to three carbonatoms.
 5. The compound as recited in claim 1 wherein R is methyl.
 6. Thecompound as recited in claim 5 wherein R¹ is an alkyl selected from thegroup consisting of methyl and ethyl.
 7. The compound as recited in anyof claims 1, 2, 3, 4, 5, or 6 wherein Y and Z are hydrogen.
 8. Thecompound as recited in any of claims 1, 2, 3, 4, 5, or 6 wherein Y and Zare chlorine.
 9. The compound as recited in any of claims 1, 2, 3, 4, 5,or 6 wherein Y is chlorine and Z is hydrogen.
 10. The compound asrecited in claim 1 which is5-(2-chloro-4-trifluoromethyl)-2-nitroacetophenone oxime-0-methyl ether.